High temperature electronics assembly using lead-antimony-tin alloys

ABSTRACT

A system for soldering electronic components capable of withstanding high temperature applications. A solder having a composition in the range between 83 and 87% lead, between 8.5 and 11.5% antimony, and the balance of tin provides superior results. The solder uniquely provides a sufficiently low melting point to enable mass flow without destruction of plastic package parts, and a sufficiently high melting point to achieve 200 degrees C. operation. Good mechanical strength is achieved while providing sufficient creep to permit differential expansion between components and a printed wiring board. A heavy solder layer is coated on a printed wiring board and is oxidized to generate a thin solderable layer. Manufacture of the circuit board can be performed with conventional techniques such as wave soldering, hand soldering, solder printing, solder dispensing, and solder pre-forms.

BACKGROUND OF THE INVENTION

The present invention relates to the field of electronics assembly. Moreparticularly, the present invention relates to a composition and methodfor soldering electronics components capable of withstanding hightemperature applications.

Electronic packages provide unique capabilities in equipment and toolspositioned in commercial and industrial applications. Increasingly, suchelectronics packages are installed in environments hostile to thesurvivability of electronics. For example, the formation temperaturedownhole in hydrocarbon producing wellbores can exceed 150 degrees C.,and such high temperatures can destroy electronic control orinstrumentation packages within hours. Many solder alloys and printedwiring board ("PWB") plating systems have been used for high temperatureelectronics applications, however such systems are limited by certainfactors. Additionally, electronic packages utilizing surface mounttechnology ("SMT") are increasingly using electronics in plasticpackages, and the long-term reliability of such packages is reduced byhigh temperature applications.

Various PWB plating processes have been developed for assemblingelectronics packages. The most common process for standard "lowtemperature" applications uses a tin/lead composition over bare copper.A copper-clad printed wiring board is dipped in or plated with a 60/40solder comprising approximately sixty percent tin and forty percentlead. The shelf life before soldering and surface solderability of thisprocess is good, however the integrity of the solder joint and PWBintegrity is destroyed at elevated operating temperatures over 100degrees C. At elevated temperatures, tin in the solder and copper on thePWB form intermetallics detrimental to long-term reliability.

The formation of intermetallics in tin/lead solders can be inhibited bythe addition of a low stress nickel barrier. A 200 micro-inch layer ofnickel prevents intermetallic formation without compromisingsolderability or shelf life. However this process is ineffective forapplications over 150 degrees C. because the tin/lead soldercontaminates the higher temperature solders, lowering the melting pointand degrading the high temperature characteristics.

Other efforts to eliminate tin and lead from the PWB have beenaccomplished by plating gold over a nickel barrier. A 50 micro-inch goldlayer prevents passivation of the nickel to provide reasonableshelf-life characteristics, and the gold dissolves in the solder uponassembly. Wave solder assembly processes perform acceptably, howevergold can accumulate in the solder pot. This accumulation requiresfrequent monitoring of pot impurities and replacement of the potcontents. When the assembly is performed by hand or by solderprinting/dispensing and mass reflow, a portion of the gold remains inthe solder and the remainder of the gold remains on the component pads.High temperature operation forms brittle gold intermetallicscompromising the mechanical and electrical characteristics of the solderjoint. Although the impact of such gold intermetallics can be moderatedby reducing the gold content, the time for passivation of the nickel andrelated unsolderability of the board is also reduced.

Another technique for incorporating the positive benefits of gold isperformed by depositing approximately 10 micro-inches of electrolesspure gold over 10 micro-inches of palladium over 200 micro-inches of lowstress nickel. Acceptable shelf life is obtained because the palladiumslows the nickel passivation and the gold slows the palladiumpassivation. This combination is preferable to a 50 micro-inch goldlayer because the overall amounts of gold and palladium dissolved intothe solder are reduced. However, this process is not conventionally usedbecause the PWB manufacturing process for this combination is morecomplex and expensive than other processes.

Another technique uses pure tin over nickel and copper. This process wasdeveloped for use with high tin solders, and uses at least 200micro-inches of pure tin deposited directly over a nickel barrier andfused to provide a low stress solderable surface. The shelf life andsolderability of this combination is excellent, however this process isunsuitable for high lead solders because the mix results in a lowtemperature solder alloy. The affinity of tin for copper reduces theprocess reliability for certain applications, limiting the utility ofthis process.

Various solders are commonly used for high temperature electronics.References to conventional solders are found in Lea, A Scientific Guideto Surface Mount Technology, Electromechanical Publications Ltd. (UK)(1988), and in Manko, Solders and Soldering, 3^(rd) Edition, McGraw-Hill(1992). The most common solder alloy is known as Sn63, having 63% tinwith a lead balance. This solder is a binary eutectic with a 183 degreesC. melting point. Although this solder is compatible with all of theplating systems described above, the mechanical strength of the alloydegrades significantly above 100 degrees C. Another common alloy knownas HMP comprises 93.5% lead, 1.5% silver, and a tin balance. This alloyprovides good results for operating temperatures over 200 degrees C.,has a solidus temperature of 296 degrees C. and has a liquidustemperature of 301 degrees C. This solder is moderately compatible withtin and lead plating provided that the solder joint volume is large suchas in wave solder applications. Another binary eutectic alloy is Sn96,having 96.5% tin and a silver balance. The melting point is 221 degreesC., it is mechanically stronger than HMP or Sn63, and retains itsstrength nearly until the melting point. The wettability is excellent,and the alloy permits mass reflow of plastic surface mount parts withoutdamage. The disadvantages of this alloy are brittleness, particularly atlow temperatures, and an affinity for copper. The brittleness results inlow cycle solder joint fatigue with repeated temperature cycling whenthe thermal coefficients of expansion of the PWB substrate and thecomponent are mismatched. For components with high copper content in thecontacts, migration of tin into the copper contact results in electricaland mechanical failure after short time periods when the exposureexceeds 150 degrees C.

As described above, tin and lead are incompatible for high temperaturesolder applications. High lead solders have high melting points and lowmechanical strength. For automated plastic surface mount assembly,exposure of such components to high temperatures destroy the components.If the solder is the only mechanism for attaching electronic componentsto the PWB, the integrity of the PWB will be compromised at hightemperatures. This limitation is particularly acute in applicationshaving shock or vibration forces. High tin solders are too brittle whenthe thermal coefficients of expansion are mismatched, and tin-copperintermetallic growth causes premature joint failure at hightemperatures. Although gold or palladium can improve the operatingcharacteristics, such materials also create brittle intermetallics overtime and generate problems in manufacture and assembly of theelectronics packages.

SUMMARY OF THE INVENTION

The present invention discloses a composition for forming a hightemperature solder suitable for electronics and electronics packageassembly. The composition comprises lead in a range between 83-87percent by weight, antimony in a range between 8.5-11.5 percent byweight, and tin substantially comprising the balance of the composition.A high temperature system for supporting electronics can comprise aprinted wiring board and solder attached to said board, wherein thesolder comprises lead in a range between 83-87 percent by weight,antimony in a range between 8.5-11.5 percent by weight, and tin in arange between 8.5-1.5 percent by weight.

The method of the invention describes assemblage of electronics towithstand high temperatures. The method comprises the steps ofpositioning a solder composition having lead in a range between 83-87percent by weight, antimony in a range between 8.5-11.5 percent byweight, tin substantially comprising the balance of the composition, andassembling the electronics with said composition. In other embodimentsof the method, a solder mask can be placed on a printed wiring board, arelatively thick layer of solder can be attached to the printed wiringboard, the thick solder layer can be oxidized to prepare a thin solderlayer, and electronics can be attached to the thin solder layer.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates a ternary antimony/tin/lead phase diagram.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The present invention provides a high temperature alloy for solderingelectronic components. The invention discloses a lead/antimony/tincombination previously unused in the manufacture and assembly ofelectronics and electronics packages. The composition of the inventionis defined as an alloy having between 83 and 87% lead, between 8.5 and11.5% antimony, and the balance of tin. This composition has beendiscovered to be uniquely adaptable to the long term survivability ofelectronics connections in high temperature environments. Thiscomposition is identified by the trademark "Innovalloy" and servicemark"Innova Process", owned by Innova Electronics, Inc. of Houston, Tex. Theperformance of the composition at different temperatures is illustratedin the ternary antimony/tin/lead phase diagram illustrated in FIG. 1 andprepared by K. Iwase and N. Aoki, Kinsoku-No-Kenkyu, Vol. 8, p. 253(1953).

This invention provides superior results as determined by tests for hightemperature, vibration, and impact test criteria. High temperatureendurance tests over 1000 hours at 175 degrees C., and temperaturecycling tests between 25 degrees C. and 175 degrees C. were comparedagainst conventional control samples, and the reliability of the testresults demonstrated significant benefits.

The relatively high lead content of the invention provides desirablecreep properties found in conventional Sn63 and HMP alloys. Leadcomprises a soft, malleable and ductile metallic element having atomicnumber 82, atomic weight 207.19, and melting point of 327.5 degrees C.Tin comprises a malleable metallic element having atomic number 50,atomic weight 118.69, and melting point of 231.89 degrees C. The lowertin content provides for wettability in normal circumstances. Antimonycomprises a metallic content provides for wettability in normalcircumstances. Antimony comprises a metallic element having fourallotropic forms. The most common form of antimony is hard, brittle,lustrous, crystalline material used in alloys with lead in batteryplates and in the manufacture of flame-proofing compounds, paints andceramic products. Antimony has atomic number 51, atomic weight 121.75,and melting point of 630.5 degrees C. The antimony in the compositionstrengthens the lead rich alloy, enhances the wetting, and depresses themelting point to permit reliable mass reflow of plastic devices. Thesolder resulting from this unique combination provides adequatemechanical strength up to 200 degrees C.

The solder defined by the composition has a nominal solidus temperatureof 239.4 degrees C. and a limit temperature of 235 degrees C. Thenominal liquidus temperature is 243.3 degrees C. and a limit temperatureof 250 degrees C.

The method of the invention removes solder plating attached to a basesuch as a PWB. This is accomplished by heating the low temperaturesolder plating to 210 degrees C. and maintaining such temperature forapproximately thirty minutes before cooling the solder plating toambient temperature. During this process, the solder melts and most ofthe solder oxidizes and turns to ash. This procedure leaves a very thinsolderable layer on the PWB.

Different solderable surfaces can be incorporated with the invention andall of the PWB plating systems described in the Background of theInvention, and others, can be used in various applications of thetechnology. In a preferred embodiment of the invention, the solderablePWB surface can comprise tin/lead over nickel over copper. Fornonsolderable areas a solder mask is placed over nickel plating.

For PWB plating, a solder mask is applied to the bare PWB after copperand nickel plating to leave exposed only the areas to be soldered.Approximately 500 micro-inches of tin/lead solder is then applied byelectroplating and fusing, or dipping and hot air leveling. Such thickcoating of the solder provides good shelf life and solderability asknown in the prior art. Surface flatness of component pads and lands isnot a concern because the bulk of the solder is removed beforesoldering. No solder is applied to other areas of the PWB such assurface interconnecting traces. This procedure avoids reflow of the lowtemperature alloy in such areas at high temperatures.

After the solder is oxidized to prepare the thin solderability layer,subsequent manufacture can proceed with conventional techniques.Although hand soldering and solder printing are the most common, wavesoldering, solder dispensing, and solder preforms are possible. Thecomposition range stated herein for tin, lead and antimony can bechanged to add trace elements or componds to vary the properties of thesolder without departing from the scope of the invention.

The solder uniquely provides a sufficiently low melting point to enablemass flow without destruction of plastic package parts, and asufficiently high melting point to achieve reliable operation at 200degrees C. for extended time periods. Good mechanical strength isachieved while providing sufficient creep to permit differentialexpansion between components and a printed wiring board. The minimalplastic range is less than 15 degrees C., and the solder is compatiblewith most existing PWB plating systems. The toxicity levels are nothigher than conventional solders, and the manufacture is relatively easyand inexpensive to perform. The solder works well with component leadshaving high copper content, nickel/iron content such as alloy 42, andother component leads having trace amounts of cobalt and coefficients ofexpansion similar to ceramics. This flexibility suits the solder definedby the invention for general purpose application in addition to hightemperature applications.

Although the invention has been described in terms of certain preferredembodiments, it will become apparent to those of ordinary skill in theart that modifications and improvements can be made to the inventiveconcepts herein without departing from the scope of the invention. Theembodiments shown herein are merely illustrative of the inventiveconcepts and should not be interpreted as limiting the scope of theinvention.

What is claimed is:
 1. A high temperature system for supportingelectronics, comprising:a printed wiring board; and a solder alloycomposition attached to said board, wherein said solder alloycomposition comprises lead in a range between 83-87 percent by weight,antimony in a range between 8.5-11.5 percent by weight, and tin in arange between 8.5-1.5 percent by weight, and wherein said solder alloycomposition provides adequate mechanical strength at temperatures up to200 degrees C.
 2. A system as recited in claim 1, wherein said board andsaid solder alloy composition are capable of reliably withstanding 200degrees C. for extended time periods.
 3. A system as recited in claim 1,wherein said printed wiring board includes a solder mask fusible to saidsolder alloy composition.
 4. A system as recited in claim 1, whereinsaid printed wiring board includes a solderable surface for attachmentto said solder alloy composition.
 5. A system as recited in claim 4,wherein said solderable surface comprises tin and lead over nickel overcopper.
 6. A system as recited in claim 1, wherein said lead comprisesapproximately 85 percent of said solder alloy composition, said antimonycomprises approximately 10 percent of said solder alloy composition, andtin comprises approximately 5 percent of said solder alloy composition.7. A system as recited in claim 1, further comprising electroniccomponents fusibly attached to said solder alloy composition.
 8. Asystem as recited in claim 1, further comprising a low temperaturesolder applied to said printed wiring board.
 9. A system as recited inclaim 8, wherein said low temperature solder is approximately 500micro-inches thick.
 10. A system as recited in claim 1, wherein saidsolder alloy composition is fusibly attached to said printed wiringboard.